Block copolymers of polymeric dianions



United States Patent 3,309,423 BLOCK COPOLYMERS 0F POLYMERIC DIANIONSGaetano F. DAlelio, South Bend, Ind., assignor, by mesne assignments, toDal Mon Research Co., Cleveland, Ohio, a corporation of Delaware NoDrawing. Filed Aug. 8, 1963, Ser. No. 300,899 17 Claims. (Cl. 260-885)This invention relates to new, reactive polymeric compositions and to aprocess for preparing them. Generally, it deals with block copolymers ofat least two monomers. More specifically, it deals with block copolymerscomprising a chain of A monomers, -6A-) as the core or nucleus of thepolymer chain, to both ends of which are attached blocks of B monomers,thus B-y tAl tB-h wherein n represents a numerical value of at 'least 4and can be as high as 10,000 or more, and m represents a numerical valueof at least one to as high as n and A and B represent the structuralunits derived from A monomers and B monomers.

It is a purpose of this invention to prepare termtAan aam blockcopolymers in which the A and B blocks differ substantially in theirchemical properties, in which the B blocks contain chemically functionalgroups which permit post-reaction to be performed selectively only inthe B block portions of the copolymer and not in the A block portion ofthe copolymer. This reactivity of the B block originates from chemicalgroups originally present in the B monomers. It is therefore a purposeof this invention to prepare block copolymers by a process wherein thefunction-ally active groups in the B monomers necessary to conferreactivity to the copolymer are not lost or caused to undergo prematurereaction of degradation in the copolymerization process.

Monomers of Class A may be written as and those of Class B as in whichR, P, and Q are fully defined hereinafter, and for the present purposesof demonstration, the A monomers may be illustrated by styrene, ethylacrylate, methyl methacrylate, etc., and the B monomers by allylmethacrylate, vinyl allylbenzoate, etc. Some of the block copolymers ofthis invention using these monomers according to the structure {-B-){-A-} {-B-} are In these illustrative block copolymers, it will be notedthat the functional group CH CH:CH is terminal in the copolymers andthat the respective cores COOCH; n

are not normally functional.

These three polymers are all reactive and can be converted to aninsoluble, infusible state by various means, such as heat alone, freeradical-generating catalysts, cationic catalysts, etc. Since thefunctional or reactive groups are terminal, they are readily availablefor postreaction, and differ in this respect from statistical or rananddom copolymers prepared from the same monomers in compared to a -GB){A-} %B9- block copolymer in which both ends are reacted and anchored,thus,

CHOH. CHzCH HaCH Polymer II oooom/s, COOOHzCH=OHg m wherein M+ is apositive counter ion, typically an alkali metal, with monomers of theformula wherein Q represents a post-react-able function, thus Thepolymer may be used as such or purified and freed of the M+ ions byWashing with water, alcohols, acids, ammonia, etc, to give It is anotherobject of this invention, in the reparation of the block copolymers ofthis invention, to graft at least one monomer of the class of monomersto each end of a polymeric dianion of the general formula -CI-I2C- andto accomplish this synthesis through an anionic polymerizationmechanism. This is in marked contrast to grafting a monomer to apolymeric mono-anion Whether or not the grafted monomer contains a Qfunction, because in such case the grafted monomer is propagated as ablock only to one end of the polymer as shown hereinabove.

By an anionic polymerization is meant a polymerization in which thepropagation occurs by the progressive addition of monomers to an anion,at a specific rate, k such as etc., in which M+ is a positive counterion, typically an alkali metal. Many such anionic polymerizations areknown.

This propagation step is preceded by an initiation step which can bebrought about in numerous ways. The anion polymerization may beinitiated by an alkali or alkaline earth metal hydride such as NaH, LiH,CaH MgH KH, CsH, etc. Such hydrides can also be in the form ofcomplexes, for example, with other hydrides, e.g., KAlH LiAlH etc.hydrides as MH, the initiating step is represented as When an alkalimetal hydrocarbon, R M, is used, the initiating step is given as inwhich case the cation M+ represents Li, Na, K, Ca, Cs, etc. and theanion, R represents a hydrocarbon radical, methyl, ethyl, propyl,isopropyl, butyl, amyl, isoamyl, cyclohexyl, benzyl, triphenyl methyl,octyl, etc., preferably containing no more than about 12 carbon atoms inthe anion. A few typical examples of MR are BuLi, (C H CNa,

(III-I3 CaH5?-K C H CH Cs, CHECNa, CH =CHCH Li, etc.

A Grignard also may be used to initiate the anionic polymerization, thusIllustrative examples of R MgX in which X is a halogen and R is asdefined above are butyl magnesium bromide, vinyl magnesium bromide,allyl magnesium chloride, phenyl magnesium bromide and chloride, etc. Inmost cases, and with most monomers, such initiations produce only monoanions which are propagated as monoanions and accordingly, the blocksoccur at only one end of the polymer chain. In most cases such blocksoffer little or no advantage over a random copolymer.

However, there are large numbers of initiating systems which producedianions in the initiating stage and these dianions propagate by thefurther addition of monomer at both ends to produce polymeric dianionssuitable for the purposes of this invention. For example, withinitiators of the formula R M, when R represents an aromatic ring suchas naphthalene, dianions are obtained. This is readily explained by aseries of reactions involving ion radicals which couple to formdianions, thus:

This same type of dianion is formed with anthracene, phenanthrene,naphthacene, acenaphthalene perylene, tetraphenyl ethylene, diphenylacetylene, stilbene, etc.

The free alkali metals can also be used to initiate anionicpolymerizations, especially when the metal, M-,

By designating such an- 6 The ion radicals couple to form a dianion,thus is added to the dimer, thus OH CH3 CH3 3 2CH2 |3-M++M-CCHtCHt(IJ-M+ OHZOHZ Znofieflkcflfi P P P 5 C0115 5H5 as a step inthe initiating mechanism. (I313 E CH3 The alkali metals in liquidammonia, and amines are 0111-0 OHtOHe CH2 also effective anionicinitiators and they can function (30m A (was (IJflHS in two ways. Forexample, in the case of potassium, sodium or calcium in liquid ammonia,the amide which The same type of dianions are produced by startingresults from the reaction of ,the metal with ammonia with styrenedimers, styrene tetramers, etc. acts as the initiator, thus 7 Anotherclass of dianions is that derived from the re- R R action of 1,3-dienes,with an alkali metal such as butadil l ene, isoprene,2-phenylbutadiene-1,3; 2,3-diphenylbuta- K NHQ IGNHZ CH3?H diene,triphenyl butadiene; tetraphenyl butadiene, etc.,

P P as illustrated by butadiene, and

, III. R CH2=CH-CH=CH2 2M MOHZCH=CHCHZM+ OHFC NHzoHzaKJ' Individualdianions are more difficult to prepare from the I l P P dime-1,3compounds than some of the other dianions H th f l f d describedhereinabove since other side reactions can oc- 2 ever m P t 0 5 an Ion10a 15 cur such as the formation of dimers, trimers, tetramers, w ichactsas em1t1ator,t us etc. For example LlfizNHfiLl (NH) i (NH3) 2Mnom=onon=orn itomoH=oHom ,M+

Where is an electron, h especially when Li metal is used which, in manyrespects, R R R R is similar to the tat-methyl styrene dianions preparedg LihCHZCHZJPLH using Li or When sodium or potassium is used, some I 1,2polymerization occurs with the dienes, such as M'P CH OH=OHCH-OH OH -M+In a similar way dianionic mitiatlon is brought about 2 2 1 by ketylswhich are the reaction products of an alkali or alkali metal with aketone such as benzophenone in CH2 ethers. Thus N In the aboveillustrations, the diamons become part of a the central block of thepolymer chain, and if the dianion l 40 is derived from a monomer WhlCh1S desired in the cenzNa 2OBHSCOOGHE 266115060115 tral block, then theblock can be prepared either in steps or in a single operation; but ifthe dianion is not derived hi h h react i h h monomer, from a monomersuch as in the case of the naphthalene R and ketyl types, or is derivedfrom a monomer 'but a central core from another monomer is preferred,then OH the block can be built up by adding at least one monomer of theclass of to form a dianion, f t Na'fiiCHzcHafil-Nti P P P monomers tothe preformed dianion. Thus it can be regenerating the ketone. Dianionsare also produced Seen that the central block when ot-methyl styrene isreacted with potassium, to pro- R s I duce a dimer, which structure isconsidered as belng (EH3 (EH3 P/HD K-CCH2CH2C-K Com 6H can be derivedfrom a single R If 1t is desired, prior to the addition of CHPJ) 1' CH 0l 5 or from a multiplicity of monomers such as when 2, 3, 4 or moremonomers are all introduced simultaneously monomers to increase the sizeof the A block, then more so that random structures e in r th m n CH3can be lntroduced consecutively so that internal regulated blocks arepresent in the central structure of the CHFC Cam 7 polymer, thus OH; HCH, CH, CH; M -H|OCH JOEz 3HzC- -lOI-I2OHz+ CHtlCH\ /GHZ+ flgCllH MCOOCzHn) \EOOCH /n \JMHE /n 05H, CuH5\ OflHfi/n COOCH3/n 0000213 insteadof a random structure.

When the dianion is initially produced from a diene such as butadiene orisoprene, it also becomes part of the polymer chain containingunsaturation which is proportional to the amount of dianion,

in the block, and the value of n in the initiating dianion. If oxidationresistance is desired in the final polymer, it is advisable to maintainthe concentration of such inter-polymerized initiators to less than20-30 percent by weight of the final polymer.

For the purposes of this invention, the origin of the initiating dianionor the mechanism by which it is obtained is unimportant, for once thedianionic system is initiated it is responsible for the polymerizationof monomers of the formula V to produce a polymeric dianion,

R M* OHFC J M+ and to this preformed dianion, propagation is continuedby the addition of monomers of the formula orn=o 5 to give the blockcopolymers of the structure,

R R R M+ CHg CHz 01-1 -M+ Q m P..,

The average molecular Weight, as expressed by the average degree ofpolymerization (DP) of the block copolymer, is given by the equation 2[Monomers] P: D [Mn in which [Monomers] represents the molarconcentration of monomers (DH-2:? and 0112 and [M+] represents the molarconcentration of the positive cation. Anionic polymerizations are alsoknown as base catalyzed polymerization.

The anionic polymerizations may be performed with the monomers of thisinvention in either the first stage in the preparation of the block, orin the second stage in the preparation of the tures, or the first stagemay be performed at either a higher or a lower temperature thanthesecond stage.

The solvents or diluents, when used, may be selected from the class ofaliphatic-and aromatic hydrocarbons, ketones, ethers and esters such asbutane, propane, hexane, heptane, octane, cyclohexane, cyclopentane,benzene, toluene, xylene, dimethyl ether, diethyl ether, dibutyl ether,tetrahydrofurane, dioxane, diphenyl ether, dibenzyl ether, dimethylethylene glycol ether, 'dibutyl ethylene glycol ether, diethyldiethylene glycol ether, etc. The diluene or solvent can also act tocontrol the molecular Weight of the polymerization by solvalitic chaintransfer with the anion when protonic solvents are used, thus pared topossess a very wide utility because of the large number of variablesthat can be readily controlled in their production. The correspondingproperties will depend in great measure on the nature and character ofthe monomers used to prepare the central block, (-A-h and whether thisblock is a homopolymeric block of only one monomer, or a randomcopolymeric block of two or more monomers alone or with other monomers,or whether it is a block within a block of two or more monomers. Theywill also depend on the ratio of the total monomers in the {-A-} blockto the total monomers in the {-Ba blocks. In the {-B-) block the type ofmonomers is important, and its activity will depend on the nature,character, and number of these monomers, whether one, two or more R @HF5 monomers are used, and whether they are added as a block within ablock or at random, etc. Accordingly, it may be appreciated that thenature of the monomers are important in the practice of this invention.Moreover, it is obvious that they cannot contain in their structuresfunctions or groups which react with or which destroy the anionicinitiating system.

Monomers belonging to Class A are monomers having only one CH =C groupand the general formula,

wherein R is selected from the class consisting of -H, CH and -CN, and Pis selected from the class of -Ar, wherein Ar is selected from the classof aryl radicals containing 6 to 12 carbon atoms and derivativesthereof, and the derivatives thereof selected from the class of alkyl,cycloalkyl and aryl groups containing no more than 12 carbon atoms;

ArY, wherein Ar is selected from the class of arylene radicals andderivatives thereof, and the derivatives thereof selected from the classof alkyl, aryl, cycloalkyl, alkoxy, aryloxyl, thioalkyl, thioaryl, and Yrepresents a radical selected from the class of OR,

SR -COOR CN, (CR COOR S (CR COOR CR OR (CR SR 2, 2 2") n 2 z n 2, z n 2O (CR CON( R NR CR COOR -N[ Z n z Rrv (OCR CR OR -CO(OCRJ'CRJMOR N(COORand SO OR wherein R is a radical selected from the class of hydrogen andR and R is a hydrocarbon radical selected from the class of saturatedaliphatic and cycloaliphatic radicals and aryl radicals and containingone to twelve carbon atoms, and n represents a numerical value of one toten;

-\COY, wherein Y" is selected from the group consisting of -S (CR COOR O(CR OR N (R 2 wherein R is selected from the class of H and R and R is ahydrocarbon radical selected from the class of saturated aliphaticradicals, saturated cycloaliphatic radicals and aromatic radicals andcontaining one to twelve carbon atoms, and n represents a numericalvalue of one to ten.

The structural unit in the polymers derived from the monomers isIllustrative examples of Class A monomers are:

OHnCH:

CH2=CHC O O CH OHQCH:

1 Q CH =CHCOOC H OCH CH =CHCOOC H OC H CH =C (CH COOCH CHFC (CH COOC HCHFC (CH COOC H C F 3) 18 37: CH C (CH COOCH C H CHFCHCOSCHCHZZCHCQSC1SH3 q, CH2:C COSC2H5, CH CHCOOCH COOCH CH =CHCOOCH COOC H CH=CHCOOCH( CH (3000 1-1 CH =C CH COOCH CH CH COOCH CH CHCOSCH COOCH CHCHCOOCH COSCH CH =CHCOSCH COSCH CH CHCOOCH CH O CH CHFCHCO (OCHgCHZ) OCHCH =C (CH 600 (CH OC H CH CHCOOCH CH N (CH CH CHCOOCH CH N C H C4H9CHFCHCOOCH CH N (C3H CHFC (CH COOCH CH N (CH CHFC CH COOCH2CH2N (C l-ICH3 C3H5) 2,

C2H5 2, CH =C (CH COOCH CON (C H CHFCHCON (CH CH =CHCON (C H CH CHCON CH 1,, CH =CHCON CH C H CH ==CHCON c n CH =C (CH CON(CH CHFC (CH3) 0 O Il (CH2) 5C 0 N(C2H5)z,

CH2=CHCON(OH2)5C O 0 CH CH3 )2, CH =CHCON[CH CON(CH 212,

I I OHFC(CH )CONCH2CHaNCHzCHzN(CH3)2,

CHFCHCN,

CHFC (CH CN,

CHZZC C6H5,

CH C (CN) COOCH CH =C COOC2H5, CH =C(CN) COOC H CH =C CN) COOC13H37,

CH =C (CN) COOCH CH OCH CH2:C COOCH2CH2CH2OC2H5, CH C (CN 0000 11 CHFC(CN) COOCH C H CH =C (CN) COOCH CO0CH CH =C (CN) COSC H CHFC (CN COOCH(CH COOC H CH =C (CN) COSCH COOCH CHFC (CN) CO (OCH CH OCH cH =c (CN)COOCH CH N (C H CH C CN) CO0CH CH N(C H CH2 C (Cal I5 2, CHFC (CN) COSCHCH N (C H v CH C (CN) CON(CH (DI-1 0 (CN) CON (C H CH C CN CON (C H CHFC(CN) CON(CH C H l CH2=CHOeH4C oNornommoznsn,

structure, as well as less readily with a variety of other monomerscontaining one or more negative suhstituents such as vinyl acetate,vinyl propionate, vinyl benzoate, dimethyl fumarate, diethyl fumarate,dimethyl maleate, diethyl maleate, dimethyl itaconate,methyl-,B-cyanoethyl acrylate, diallyl maleate, diallyl fumarate,diallyl itaconate, etc., in which case any unconverted monomer can beremoved by distillation or extraction, or even be 'allowed to remainadmixed with the polymeric dianion during the second stage of graftingof the B monomers. In other cases, these monomers, which react poorly orvery slowly, can be used as the solvent for both phases of the reaction.

The monomers of Class B have the general formula CHZ=(IJ Q,

wherein R is selected from the class of H, CH and CN; Q is selected fromthe class consisting of -A1'D, in which -AI- is selected from the classconsisting of arylene radicals and the derivatives thereof, in whicheach derivative is selected from the class consisting of alkyl, aryl,cycloalkyl, alkoxy, aryloxy, and cycloalkoxy groups, D represents aradical selected from the class consisting of (CR R", OR", SR",

(OCR' CR' OR, CO (OCR CR OR" -N(COOR") and SO OR'", in which R is aradical selected from the class consisting of hydrogen and hydrocarbonradicals containing one to ten carbon atoms and R", R" is a radicalselected from the class of alkenyl, alkenyloxyalkyl, andalkenylthioalkyl radicals, said radicals containing two to ten carbonatoms and possessing a terminal CH C group, R" is a radical containingone to twelve carbon atoms of the class consisting of hydrocarbon,alkenyloxyalkyl and alkenylthioalkyl radicals, and n represents anumerical value of one to ten.

(Monomers of the formula are disclosed in my copending applications Ser.Nos. 300,902 and 300,939 filed the same date herewith.)

ArNCS;

COD, in which D is selected from the class consisting of OR", SR, O(CR'),,COOR,

--(OCR' CR' OR", in which R,R", and R" are as defined above.

15 CH =C CN) C H COOCH CH=CH GHZ=O(CN)CBI'IQCOOOII2?=CITE.

CH This invention will be more fully described by the followingexamples. The invention is not to be regarded, however, as restricted inany way by these examples and they are to serve merely as illustrations.In these examples, as well as throughout the specification, parts andpercentages shall mean parts by weight and percentages by weight unlessspecifically provided otherwise.

Example I with a 5? value of about 15 and a molecular weight of about1550. The dianionic nature of the polymer is proven readily by reactionwith carbon dioxide according to Nature, 178, 1168 (1956), and J. Am.Chem. Soc., 78, 2656 (1956) to give Part B.If in this procedure there isadded originally 31.2 parts of styrene, or if an additional 15.6 partsof styrene are added after the original addition, then the dianion willbe of an average molecular Weight twice that of the original dianion,thus Part C.If a total of 156 parts of styrene in 1500 parts oftetrahydrofurane are used, then the molecular weight of the polymericdianion is correspondingly larger, thus Part D.However, if 15,600 partsof styrene in 25,000 parts of tetrahydrofurane are used, the dianion isPart E.Alternately, when the amount of initiator is increased, such aswhen two equivalents of lithium naphthalene are used with 416 parts ofstyrene in 1200 parts of tetrahydrofurane, the average value of E in thedianion is 4, or

Example 11 Example I is repeated using equivalent quantities of sodiumnaphthalene, potassium naphthalene, and cesium anthracene and thecorresponding dianions,

are obtained.

15 Example III In a. suitable reactor containing a dry nitrogenatmosphere, are placed 150 parts of distilled and 4 parts of metallicpotassium in pellet form, and the reaction allowed to proceed at 15l7 C.for 12 hours with continuous agitation. Then the viscous mixture isfiltered to remove any unreacted potassium and the solution consists ofabout parts of unreacted alpha methyl styrene and about 75 parts of thepolymeric dianion,

The excess alpha methyl styrene can be removed by vacuum distillation ata pressure of 1 mm. or less, and the inherent viscosity of 0.5% solutionof the isolated polymer in toluene at 25 C. is about 0.74. The excessunreacted alpha methyl styrene can also be separated from the polymericdianion by extraction with liquid hexane, and the dianion dissolved intetrahydrofurane for further reaction.

Alternately, the procedure of Examples I and II can be used withtetrahydrofurane as the solvent for the reaction and the polymer allowedto remain in solution without isolation and used for further reactions.

When equivalent amounts of lithium or sodium are substituted in theprocedure of this example, similar results are obtained. However, therates differ and their speeds are in the following order K Li Na, and anincrease in reaction time is necessary it higher conversions arerequired.

Example IV The procedure of Example I is repeated using equivalentamounts of sodium benzophenone and the equivalent dianions,

Example V The procedure (Part A) of Example I is repeated usingequivalent amounts of acrylonitrile (7.95 parts= millequivalents) andthe corresponding polyacrylonitrile dianions,

are obtained.

hydrofurane as the solvent, then the polymeric dianion is obtained insolution.

Example VI Example V is repeated using dimethyl formamide as the solventand 10.35 parts of methacrylonitrile, and there is obtained in solutionthe polymeric dianion,

in Ll -CH2C -Li+ Example VII Example VI is repeated using 14.4 parts ofcyanomethyl acrylate and there is obtained the polymeric dianion,

3,309,423 1 7 18 Example VH1 Example XIII Example V1 is repeated using12.75 parts of The procedure (Part C) of Example I is repeated using CHON 2 CHC F i 104 parts of styrene, and after the addition of the styreneand them Obtamed the polymer: dlamon 5 is completed there is added 172parts of ethyl acrylate.

After its addition is completed there is added 284 parts 1+'CH2CH--Ll+ Lj of butyl methacrylate, and there is obtained the tripolymer LON(CH3)2n block A Example IX Example XIV To 50 parts of tetrahydrofurane isadded 0.75 part of ggif g gfigg gi gi g 32: 3; 55;1 :32 butadiene and0.14 part of finely divided metallic lithium, is obtained the dianionic01 mar and the mixture allowed to stand at room temperature P y untilthe metallic lithium disappears and there is obtained a mixturecomprising substantially LiCH CH=CHCH Li,

and to this mixture is added, after cooling to 40" C., I j 2400 parts oftetrahydrofurane and 1000 parts of styrene. 000cm The reaction iscontinued for 18 hours and there is obtained a dianion polymer, ExampleX Li+-C HC H2C HzOH=OHCHz-C HzC H-Li+ The procedure (Part C) of ExampleI is repeated using H I H j 150 parts of methyl methacrylate instead ofthe styrene 5 n 5 and there is obtained the polymeric dianion, ExampleXV CH3 1 The procedure of Example V is repeated using dimethyl formamideas the liquid medium containing a mixture of 7.95 parts ofacrylonitrile, 2.4 parts of ethyl COOOHs/A acrylate and a randomcopolymer dianion,

The procedure (Part B) of Example I is repeated using is obtained 43parts of ethyl acrylate to produce the dianionic polymer, 7 Example XVIl v The formation of the di-block from polymeric dianions is illustratedby using polymer A of Example I, adding K cm, to the solution of thedianion, at 77 C., 2.24 parts of. allyl acrylate, and allowing thereaction to proceed for and then without isolating the product, 100parts of 45 two hours. There is obtained the polymer methyl methacrylateare added to produce the A block having the structure CH CH at 3 l aThlS 1s confirmed by brom1nat1on 1n toluene of a sample "T 1 of thepolymer isolated by precipitation of an aliquot COOCzI-Is n 00002115 nCOOCzHs n. part of the solution in methanol to give the derivativeHJCHCIL /"H2CH CHzCH H Example X11 1 By further addition to the solutionof an additional The procedure (Part B) of Example-I is repeated using31.4 parts of allyl acrylate there is obtained the di-block a monomermixture of 43 parts of ethyl acrylate and of approximate composition 50parts of methyl methacrylate and a random copolymer The solution is thenneutralized with acetic acid and A block containing structure units ofboth monomers is filtered. To a sample of the solution is added 0.1%obtained, benzoyl peroxide by weight of the polymer and films cast onglass. The solvent is allowed to evaporate at 50 C.

, OHa and the solvent-dried film heated at C. for 30 minl, utes. Testswith benzene, toluene, acetone, dioxane, and

\ ether confirm that the polymer film is insoluble and COOCHa COOCH: n 7infusiblel 1 9 Example XVII Example XVI is repeated using polymers ofParts B, C, D, and E of Example I with 2.24 parts of allyl acrylatefollowed by an additional 31.4 parts of allyl acrylate, and di-blockcopolymers containing post-reactive B blocks at the ends of the chainsare obtained in all cases;

Example XVIII Qualitative tests are made using the procedure of ExampleXVI with polymer A and. parts of each of the following B monomers:

In all cases, insoluble, infusible polymers are obtained when thepolymers are heated at 125-130 C.

Example XIX In a suitable reactor equipped with stirrer is charged 300parts of styrene and 3000 parts of hexane under an inert anhydrousnitrogen atmosphere at a temperature of 25 C. To this solution is added3 millimoles of naphthalene-lithium and the temperature rises to about45 C. Stirring is continued for six hours at 2530 C. The reducedviscosity of the polymer at this stage, isolated from an aliquot part ofthe solution and determined at 30 C. at a concentration of 0.2 gm./100cc. benzene, is 0.18. The solution is then cooled to C., 100- parts ofallyl methacrylate are added, the mixture is stirred for an additional 4hours at 10 to -5 C. for 4 hours, and then allowed to come to roomtemperature. The solution is then added to methanol (10,000 parts) andthe resultant white precipitate is the di-block copolymer filtered anddried to yield 400 parts of product having a reduced viscosity of 0.48when 0.2 gm. of the di-block is dissolved in 100 ml. benzene at 30 C.

Example XX Ten parts of the polymer of Example XIX are dissolved in 30parts of a mixture of 10 parts of dioxane and parts of toluene. A filmis cast on glass from part of the solution, and the solvent allowed toevaporate therefrom at room temperature. At the end of 48 hours the filmis still soluble in acetone, toluene, dioxane, and carbon tetrachloride.

When a portion of this film is (a) heated at 150 C. for 30 minutes or(b) irradiated with a van der Graaf linear accelerator or a cobalt 60source to a dose of 5 or more megareps, the films become insoluble inthese same solvents. To another portion of the solution is added benzoylperoxide in an amount to correspond to 0.5% by weight of the polymer. Afilm is cast from this solution and the solvent is allowed to evaporateat room temperature for 48 hours. When this latter film is heated at135-150 C-. for two minutes, it becomes insoluble and infusible.

20 Example XXI Impregnated sheet stock is prepared by dipping sheets ofcellulose paper in the polymer solution of Example XX containing benzoylperoxide, and the sheets dried at C. for 15 minutes. Six sheets aresuperimposed and placed between the platens of a press and heated to C.for 15 minutes at a pressure of 200 p.s.i., and a wellbonded, thermosetlaminated product obtained.

Example XXIII To a solution of 10 parts of the polymer of Example XIXand 30 parts of tetrahydrofurane is added 0.1 part of benzoyl peroxideand 2 parts of allyl monoitaconate,

and films prepared on freshly sanded iron, steel, copper and aluminumsheets and cured at C. for 1 hour. In all cases, the coating yield isquantitative and the bond of the films to the sheets is excellent.Instead of monoallyl itaconate, other acidic monomers such as acrylicacid, methacrylic acid, maleic half esters, etc., are used and similarresults are obtained.

Example XXIV Ten parts of the polymer of Example XIX are mixed with 20parts of commercial divinyl benzene (a 50-50 mixture of divinyl benzeneand ethyl vinyl benzene) containing 0.3 part of benzoyl peroxide. To theresulting viscous mixture is added 30 parts of ground mica to form aputty which is molded at 140 C. at a low pressure of 30-100 p.s.i. intoheatand solvent resistant structures. Similar results are obtained whenthe divinyl benzene is replaced by allyl methacrylate, glycoldimethacrylate, diallyl itaconate, diallyl fumarate, diallyl maleate,divinyl phthalate, diallyl phthalate, or divinyl succinate, etc.

XXV

Glass-woven fabric is dip-treated with a solventless commercial, liquid,unsaturated resin (50% styrene-50% phthalic modified glycol maleatecontaining 0.5% peroxy catalyst) in which is dissolved 10% by weight ofthe polymer of Example XIX. The coated fabric is converted to a glasslaminate by stacking 4 sheets between metal platens coated with zincstearate and cured at 120 C. at 10 p.s.i. The laminate containing thepolymer of Example XIX cures in less than 15 minutes and is more stiffand more heat-resistant than a similar laminate made from the samepolyester not containing the polymer of Example XIX.

Example XXVI To a mixture of 35 parts of toluene and 5 parts of acetoneis added 15 parts of the polymer of Example XIX, 2 parts of allylmonoitaconate, 1 part of diallyl maleate and 0.5 part of2,2'-azobis-isobutyronitri-le and the mixture stirred until homogeneous.The inside of a clear iron pipe of 3' ID. is centrifugally spray-coatedwhile the pipe is heated to 80 C. and rotated, the solvent is allowed toevaporate and the temperature raised to C. Curing is continued for about5 minutes. A solvent-resistant, heat-resistant, internal coating of goodquality is obtained.

4 $309,423 21 22 Example XXVI] Example XXX Example XXIX is repeatedusing instead of glycidyl Continuous strips of aluminum are coated withthe acrylate, the monomer polymer solution of Example XXVI and heated to60 C. CH =CHC O OCH GHCH The solvent-dried but uncured sheets arefabricated into 5 2 2 2 cans by the process of US. Patent 2,982,457, May2, 1961. After forming the fabric sheets are clamped while H-O-O3H1 onthe {nandrll and heated f 30 fi and the resulting polymer exhibitstenacious adhesion to Heat-resistant, tubular laminated cans areobtained. ll l metals, and especially 1. w the When the treated stripsare spiral-wound and then heat- O O OH CHCH treated as in the making ofthe can, then continuous 2T a pipe is produced. Similar results areobtained when copper, iron, silver, e'tc., metals are processed in thesame H C C3H1 Way as the alummum Smps' used in this example is replacedby related monomers,

such as CH2=OHCOOCH2CHOH2 Example XXVIII An enamel is produced by addingmilled TiO pigment to the polymer solution of Example XXVI so that theCH =CHCOOCHzCHGH2,OH2=CCOOCI-I2CHCH2 pigment-binder ratio is 60-40. Thefaces of surfaceground concrete blocks are coated with the enamel, thesolvent is allowed to evaporate at 60 C., and the coated H"O CHB CH3CCH3 blocks are heated at 180 C. for 15 minutes in a continuetc., andsimilar results are obtained. ous oven. A glassy, porcelain-like finishwhich is Water, heat, and solvent resistant is obtained on each block. AExample XXXI similar finish is obtained with this enamel on oak, maple,Example X 1S repeated Instead of y y cedar, pine, and mahogany panels,as well as on fiberacrylate There 15 used ([116 monomer boards, asbestospanels, and concrete castings. CH2=CHCOOCH2CH2N(CH3)2 The resultingcured films exhibit great adhesion to metals,

glass, ceramics, and especially to cellulose products.

. Similar improved properties are obtained when the N,N-

Example XXIX dimethylaminoethyl acrylate is replaced byrelated mono.

mers such as To a mixture of 35 parts of toluene and 15 parts of CH=CHCOOCH CH U(C H acetone is added 15 parts of the polymer of ExampleXIX, 40 CH =C(CH )C0OCI-I CH N(CH and 0.5 part of benzoyl peroxide; andit is stirred until CH =C(CH ),COOCH CH N( C H homogeneous. There isthenadded 2 parts of. glycidyl (II-1 :0(CH )COOCH CH N(C H acrylate andfilms prepared on 'freshly sanded, surface CH =CHCOOCH CH N(C H oxidizedsheets of iron, copper, brass and aluminum. CH CHCOOCH CH N(C H Thesheets are cured at 160 C. for 2 hours, and an ex- CH =C(CH )COOCH CHN(C H) m cellent bond is formed between the polymer and the metal. Goodresults are also obtained when 0.5, 1.0, and Example X 1.5 parts ofglycidyl acrylate are used instead of 2 parts, The procedure of ExampleXIX is repeated using 600 with slightly improved bonding being evidentwhen 1.5 parts of methyl methacrylate instead'of 300 parts of and 2.0parts are used over that obtained with 0.5 and styrene. The isolateddi-block copolymer 1.0 part. Similar results are obtained when insteadof is converted to insoluble, infusi'ble products by the proglycidylacrylate, there is used cedures of Examples XX and XXXI inclusive withsimilar OLIFOHOQHSOHGIh, OI-I=C(OH3)COOCHCHCH2 results.

(3N CH2=C-COOH CHz=C-OOOCI-IC\H/CH- O moooomgH om Example XXXIII O E Theprocedure of Example XIX is repeated using 60 CHi=C-C00OH2CHCH2 parts ofCH =CHC H COOCH CH=CH instead of 100 parts of allyl methacrylate and theisolated di-block coetc. I polymer H/CHCIL HsCI-I CHzCH H converted tothe insoluble, infusible products by the procedures of Examples XX toXXXI inclusive. Similar results are obtained.

Example XXXIV Similar insoluble polymer products are obtained whentreated by the procedures of Examples XX to XXXI inclusive.

Example XXX V The procedure of Example XIX is repeated using 300 partsof styrene and 15 parts of CH :CHC H CH CH==CH A quantitative yield isobtained of the di-block polymer which is readily converted toinsoluble, infusible products by the procedures of Examples XIX to XXXIinclusive.

Example XXXVI To 40 parts of toluene is added 10 parts of the polymer ofExample XXXV and 01 part of benzoyl peroxide. Films are cast on uncoatedcellophane, dried at 60 for 10 hours and cured for 3 hours at 150 C.,and an insoluble, infusible film, 15 mils thick, is obtained in eachcase which is separated from the cellophane by immersion in water andthen redried. In each case, parts of the dried film is immersed in asuitable reactor in an excess of fuming sulfuric acid (70% H 80 30% S0at 25 C. for 14 hours, then washed with dilute sulfuric acid andfinally, with distilled water until free of H 50 and tested as an ionexchange resin. The resultant capacity is found to be equivalent to one-SO H group per each benzene ring.

Example XXXVII The dianions of Examples V to VIII, and XI to XV areconverted to di-blocks with allyl acrylate by the procedure of ExampleXVI, and heat-curable di-blocks are 24 Example XXXVIII Ten parts of thesoluble, fusible di-block copolymer of Example XXXII are dissolved in 2parts of diethyl fumarate and 15 parts of methyl methacrylate containing0.1 part of benzoyl peroxide and the mixture is cast in a rod mold at 60C. for 72 hours. The resulting rod is clear, hard and insoluble inacetone, benzene and carbon tetrachloride.

Example XXXIX The dianions of Examples V to VIII and XI to XV areconverted to di-blocks with 12.8 parts CH2=CHCOOGH2CHOH2 0 0 crrs c cHaby the procedure of Example XVI. The polymers are isolated anddry-blended with 4 parts metaphenylene diamine and heated at C. for 4minutes. Infusible, insoluble polymers are obtained.

Example XL Example XXXIX is repeated with the same dianions but with11.4 parts of CHQ=CHCOOCHQCHCH2 instead of GH=CHOOOOH2CHCH2 0 0OHa-C-OHa Insoluble, infusible polymers are obtained when the polymersare mixed with (a) 4 parts of metaphenyldiamine, (b) 3 parts of phthalicacid or 1 part of zinc chloride.

Example XLI Example I is repeated to prepare the polystyrene dianion ofDP of about 50, and then 270 parts of methacrylyl caprolactam,

CI-Iz=( 3CON are added and the reaction continued at 20 C. for 4 hours.solution precipitated in methanol and the di-block Ira 221a,.

H\C (Eliz (3111011 /m I /m M 00115) i M NOO CON CO filtered and dried invacuum. The dried polymer is mixed with 6% by weight ofmetaphenylenediamine and on heating to C. becomes insoluble andinfusible.

Example XLII obtained in all cases.

A311 H-COIL CH2 CH3 CH3 (AHIL) am ear H \booomorhom/m CH 1,115).JO0OHaCH=CHz/m 0 I em CON Then the Li is neutralized with acetic acid,the

is obtained when isolated by the procedure of Example XLI.

The dried polymer is mixed with 0.1% benzoyl peroxide and on heating to150155 0., becomes insoluble and infusible.

Example XLIII range of utility for a number of reasons.

They can be prepared in the fluid liquid, or moderately viscous, orhighly viscous, or solid form; the permissible range ofcopolymerizations can involve two or three or more mnomers, even up to10 or 20 if desired. In the uncured state they can be brominated and/orhalogenated and converted to self-extinguishing polymers.

They can be used as impregnants for all sorts of porous bodies orstructures.

They are useful as coating compositions and adhesives. They can bemolded or heat-formed into infusible structures alone or with organic orinorganic fillers, including finely ground dusts as well as fibers. Theycan be converted to reinforced glass laminated structures alone or asmodifiers for the unsaturated polyesters. They can be cast intointricate shapes and can be blended or otherwise compounded with othernatural and synthetic oils, pitches, resins, and polymers. Some can bespun from solutions into fibers and then converted to heat and resistantfibers, flocks, and woven products. They can be post-modified with othermonomers to improve their adhesive or bonding properties withoutimpairment of their heat-resistant properties.

While certain features of this invention have been described in detailwith respect to various embodiments thereof, it will, of course, beapparent that other modifications can be made Within the spirit andscope of this invention and it is not intended to limit the invention tothe exact details shown above except insofar as they are defined in thefollowing claims.

The invention claimed is:

A linear block copolymer having the formula wherein 11 represents anumerical value of at least 4, m represents a numerical value of atleast 1, R is selected from the group consisting of H, CH

and CN,

is selected from the group consisting of Ar, ArY', COY",

Q is selected from the group consisting of ArD,

and

'26 aryl groups containing no more than 12 carbon atoms,

Aris selected from the class consisting of arylene radicals containing 6to 12 carbon atoms and derivatives thereof and the derivatives there ofselected from the class consisting of alkyl, aryl, cycloalkyl, alkoxy,aryloxy, thioalkyl, and thioaryl containing no more than 12 carbonatoms,

Y' represents a radical selected from the class of OR', SR COOR CN, O(CRCOOR S (CR COOR 2 )n 2 )n 2 )n )2, -CON( )z, 2 )n )2: 2 )n )2, 2 )n )2,

Y" is selected from the group consisting of OR', SR O(CR )C00R COD'represents a radical in which D is selected from the class consisting ofOR, SR", (OCR' ),,COOR, S(CR' ),,COOR, O(CR' OR",

R is a radical selected from the class consisting of hydrogen andhydrocarbon radicals containing 1 to 10 carbon atoms and R", R" is aradical selected from the class of alkenyl, alkenyloxy alkyl, andalkenyl thioalkyl radicals, said radicals containing 2. to 10 carbonatoms and possessing a terminal R is a radical selected from the classconsisting of hydrocarbon radicals containing 1 to 12 carbon atoms andR",

R is a hydrocarbon radical selected from the class consisting ofsaturated aliphatic and cycloaliphatic radicals and aryl radicals, andcontaining 1 to 12 carbon atoms,

R is a radical selected from the class consisting of hydrogen and R,

R represents a radical selected from the group consisting of H and -CH nrepresents a numerical value of 1 to 4.

2. A block copolymer of claim 1 which comprises the CH2(3H repeatingstructure in the l -CH2-(|3- structural unit and the repeating structureH -CH2(I3-- COOOHzCH=CH2 in the R -CH J- P and Q being defined as inclaim 1.

3. A block copolymer of claim 1 which comprises the repeating structure,

28 structural unit, and the repeating structure,

CGHAC 00 C H2CH=CH2 in the R O H2 structural unit P and Q being definedas in claim 1.

5. A block copolymer of claim 1 which comprises the repeating structure,

CHz-OH in the R -CH2-- structural unit, and the repeating structure,

-CH2CH (IJBILQOOIIZCII=CHZ in the CHzN( 3- structural unit P and Q beingdefined as in claim 1.

6. A block copolymer of claim 1 which comprises the CHzCI-I- repeatingstructure in the R OHZ(IJ- structural unit, and the repeating structure,

-CH2CH GsH4CI'IzCI'I=CH5 in the R CH2( J structural unit P and Q beingdefined as in claim 1.

7. A block copolymer of claim 1 which comprises the repeating structure,

8. A block copolymer of claim 1 which comprises the repeating structure,

in the R -CHz( 1 structural unit, and the repeating structure crn -CH JCOOOHzOH=OH2 in the R --CH2-('!)' structural unit P and Q being definedas in claim 1.

9. A block copolymer of claim 1 which comprises the repeating structure,

structural unit, and the repeating structure CI-TrCH- CaH4COOCHzCH=CHzin the R -CHz(!1- structural unit P and Q being defined as in claim 1.

10. A block copolymer of claim 1 which comprises the repeatingstructure, 7

. CH3 -CH2-(!J in the t -CHn( 1 1' structural unit, and the repeatingstructure 6H4CH2CH=CF2 in the l R CHz( 3 structural unit P and Q beingdefined as in claim 1.

11. A block copolymer of claim 1 in which comprises repeating structure,

H -CH2-(|J- in the structural unit, and the repeating structure CH2CH C0 OCH2CH=CH in the structural unit P and Q being defined as in claim 1.

12. A block copolymer of claim 1 which comprises the repeatingstructure,

(3o 0 OH; in the R CH2(|3 structural unit, and the repeating structureCHz-CH OOOHzCH=CHa in the R win-( structural unit, and the repeatingstructure -CHzCH OOCHzCH=OH2 in the R -CH2--( structural unit P and Qbeing defined as in claim 1.

14. A blockcopolymer of claim 1 which comprises the repeating structure,

CH CH C O 0 CH3 in the R C Hg-()- 1% structural unit, and the repeatingstructure 0 Ila-( O 0 01120 H=CH2 in the R C H2(IJ- structural unit Pand Q being defined as in claim 1.

15. The process of preparing the block copolymer of claim 1 whichcomprises reacting at least one monomer of the structure with apolymeric dianion of the structure i -OH2([1" P n 1 P and Q beingdefined as in claim 1.

16. The process of converting the block copolymer of claim 1 to theinsoluble, infusible state Which comprises heating the polymer in thepresence of a radical generating 15 catalyst.

17. The process of converting the block copolymer in claim 16 to theinsoluble, infusible state in the presence of another ethylenic monomer.

References Cited by the Examiner UNITED STATES PATENTS Walling et al.26086.1 Johnson et al. 260-867 Jen 260-885 Hwa et al. 260-885 Baer eta1. 260885 Felinski et a1 260885 Volment et al. 26086.7 Zelinski et al260-879 Canada.

MURRAY TILLMAN, Primary Examiner.

J. T. GOOLKASIAN, Assistant Examiner.

1. A LINEAR BLOCK COPOLYMER HAVING THE FORMULA